CN103772169A - Method for synthesizing low-impurity content glyoxal through gas phase oxidation - Google Patents
Method for synthesizing low-impurity content glyoxal through gas phase oxidation Download PDFInfo
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- CN103772169A CN103772169A CN201410048613.2A CN201410048613A CN103772169A CN 103772169 A CN103772169 A CN 103772169A CN 201410048613 A CN201410048613 A CN 201410048613A CN 103772169 A CN103772169 A CN 103772169A
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- silver
- copper
- glyoxal
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- gas phase
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229940015043 glyoxal Drugs 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 239000012535 impurity Substances 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 97
- 239000004332 silver Substances 0.000 claims abstract description 97
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 91
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 238000007747 plating Methods 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 238000005234 chemical deposition Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- -1 silver ions Chemical class 0.000 claims description 7
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 6
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000012493 hydrazine sulfate Substances 0.000 claims description 5
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000001465 metallisation Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention belongs to the technical fields of chemistry and chemical engineering and in particular relates to a method for synthesizing low-impurity content glyoxal through gas phase catalytic oxidation. The method comprises the following steps: taking crystallized silver prepared by an electrolytic process as a carrier; performing high-temperature treatment, performing metal deposition, drying and roasting to obtain crystallized silver containing copper-silver alloy particles; taking the crystallized silver loaded with the copper-silver alloy particles as a catalyst, carrying out an oxidizing reaction among ethylene glycol, oxygen, water and inert gases to generate glyoxal in the presence of a catalyst. The 40 percent of glyoxal aqueous liquid in which the formaldehyde content is less than 500ppm and the glycolaldehyde content is less than 0.5 percent is directly obtained by performing air oxidation on ethylene glycol. The catalyst is easily regenerated and can be regenerated with a similar electrolytic silver method, and the prepared glyoxal is high in product quality.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for synthesizing low-impurity-content glyoxal by gas-phase catalytic oxidation of ethylene glycol.
Background
The production of glyoxal by the reaction of ethylene glycol with air over a silver or copper catalyst is the primary route for glyoxal production and research work on ethylene glycol air oxidation catalysts has been ongoing for decades. The German patent DE1,967,147 takes the crystalline silver as the catalyst, the yield of the synthesized glyoxal can reach 70%, but the conversion rate is not ideal enough, and the space velocity of the raw material is low. The US patent No. 4,242,282 adopts crystallized silver with particle size of 0.1-2.5mm as catalyst, the catalyst has a filling thickness of several cm, the reaction gas residence time on the catalyst is greatly shortened, the space velocity of the raw material is several times that of the catalyst, the catalytic efficiency is greatly improved, but the yield of glyoxal is only 55%. The US patent US4,511,739 improves the process of US4,242,282 by absorbing hot product gas with water or aqueous glyoxal solution, the yield of glyoxal is increased from 55% to 62%, the conversion of glycol is 98%, by using this process 40% commercial aqueous glyoxal solution can be obtained directly, and the product color is also much lower than the previously described process. In order to increase the activity of the catalyst, researchers have replaced crystalline silver catalysts with copper silver catalysts. In the British patent GB1,272,592, copper-silver alloy is used as a catalyst, the yield of the glyoxal synthesized by the gas-phase oxidation of the ethylene glycol is 55-72%, but the conversion rate of the ethylene glycol serving as a raw material is low, and the space velocity of the raw material is low, so that the quality of the product is influenced. The U.S. Pat. No. 4, 4,258,216 uses copper-silver catalyst, and adds bromine as promoter to the raw material, the yield of glyoxal is as high as 80.5%, but the added bromine has strong corrosion action in the presence of oxygen, and the catalyst is deactivated quickly. In order to increase the service life of copper-silver catalysts, British patent GB1,361,190 uses an excess of oxygen to treat the catalyst and regenerate it, but this method does not increase the single-pass life of the catalyst. The U.S. Pat. No. 4,503,261 describes layering a copper catalyst and a crystalline silver catalyst, the catalyst bed comprising one or more layers of the copper catalyst and one or more layers of the crystalline silver catalyst, the copper and silver catalysts having a particle size of 0.1 to 2.5mm, and the method shows better catalytic activity and stability than the use of the silver catalyst alone or the copper catalyst alone. Chinese patent ZL200710038313 adopts chemical plating to load copper on the surface of crystalline silver, compared with the catalyst, the chemical plating copper-loaded crystalline silver shows very high conversion rate of glycol and yield of glyoxal, the stability is also obviously superior to the catalyst reported in the patent, but the content of formaldehyde and hydroxy acetaldehyde which have important influence on the product quality is still higher. For glyoxal products, along with the technical progress, the requirements on the product quality are higher and higher, particularly the requirements on the contents of impurities formaldehyde and hydroxyacetaldehyde in the products are tighter and tighter, and the significance of producing the glyoxal products with low impurity content is important. The commercial glyoxal product is a 40% aqueous solution that cannot be purified by rectification and requires increased selectivity and suppressed formation of impurities, mainly formaldehyde and hydroxyacetaldehyde, during the reaction stage. On the above-disclosed catalyst, the formaldehyde content in the product was greater than 1000ppm and the hydroxyacetaldehyde content was greater than 0.5%, which is unacceptable for high quality glyoxal. The chemical plating of copper-loaded crystalline silver disclosed in ZL200710038313 has very small surface of crystalline silver, and copper is deposited on the smooth surface of crystalline silver, covering part of the active surface of silver, resulting in poor selectivity. In addition, the surface-deposited copper and bulk crystalline silver do not readily form a solid solution with atoms intercalated into the lattice of the other, which has good activity. The invention aims to provide an improved method for preparing a catalyst for loading copper-silver alloy particles on crystalline silver, which has high conversion rate of glycol and yield of glyoxal, and can directly receive and obtain a high-quality glyoxal product with low impurity content of 40%, wherein the formaldehyde content in the product is lower than 500ppm, and the hydroxy acetaldehyde content in the product is lower than 0.5%.
Disclosure of Invention
The invention aims to provide a method for preparing high-yield and high-quality gas-phase oxidation synthesis low-impurity-content glyoxal.
The method for synthesizing the low-impurity-content glyoxal by gas phase oxidation selects a commercially available crystalline silver catalyst or crystalline silver prepared by an electrolytic method described in a plurality of literatures as a carrier; firstly, carrying out high-temperature treatment on crystalline silver in the presence of water vapor, wherein crystal face reconstruction is carried out on the crystalline silver, a smooth surface is changed into a rough surface which is suitable for being used as a suitable carrier of metal particles, and the exposed crystal face is mainly a 111 crystal face; then ultrasonic treatment is adopted during metal deposition, and the nucleation speed of the metal is greatly accelerated under the action of ultrasonic waves, so that copper ions and silver ions are uniformly reduced and deposited on the rough surface of the crystalline silver to form high-dispersion particles instead of a plating layer, and the crystalline silver combined with the stable copper-silver-loaded alloy particles can be prepared after drying and roasting and is used as a catalyst for synthesizing low-impurity-content glyoxal through gas phase oxidation.
The method for synthesizing the glyoxal with low impurity content by gas phase oxidation comprises the following specific steps:
(1) placing the crystallized silver in a fixed bed reactor or a tubular furnace for heat treatment, filling the crystallized silver in a reaction section, pumping distilled water into a gasifier by a metering pump to form steam, mixing the steam with preheated air, performing overheating and temperature rise, and then entering the reaction section for pretreating electrolytic silver, wherein the liquid hourly space velocity of the distilled water is 10-50hr-1The air flow rate is 0.002-0.011M per gram of crystalline silver3The pretreatment temperature is 300-; stopping steam after the heat treatment is finished, then cooling the electrolytic silver under the air flow, and in the process, driving out the water vapor in the reactor or the tubular furnace to finally obtain dry treated electrolytic silver;
(2) placing the treated electrolytic silver in a deposition pool with an ultrasonic function to carry out metal particle chemical deposition; washing and drying the deposited copper-silver-loaded crystalline silver, and roasting at 400-700 ℃ for 2-6 hours to obtain copper-silver alloy particle-loaded crystalline silver;
the plating solution for chemical deposition consists of copper ammine complex ions, silver ammine complex ions, sodium hydroxide, ammonia water and a reducing agent;
(3) taking the crystallized silver loaded with the copper-silver alloy particles as a catalyst, and carrying out oxidation reaction on ethylene glycol, oxygen, water and inert gas (such as nitrogen) on the catalyst at 400-800 ℃ to generate glyoxal; wherein,
the ethylene glycol is subjected to oxidation reaction in the presence of inert gas (such as nitrogen), and the molar ratio of the inert gas to oxygen is not less than 4.4: 1; the molar ratio of oxygen to ethylene glycol is 0.7: 1-1.4: 1; the liquid hourly space velocity of ethylene glycol on the catalyst is 5-50 hr-1。
The grain size of the crystallized silver is 0.1-2.5mm, and the crystallized silver is paved in 2 layers or multiple layers according to the grain size, and preferably 3-6 layers.
In the step (2), the preparation method of the electroless plating solution comprises the following specific steps:
(a) dissolving copper nitrate and silver nitrate in distilled water, and adding excessive ammonia water while stirring after the copper nitrate and the silver nitrate are completely dissolved to form a mixed solution of a copper ammonia complex and a silver ammonia complex;
(b) adding a reducing agent into distilled water, adding sodium hydroxide if necessary, and stirring for dissolving;
(c) and mixing the two solutions to obtain the chemical plating solution for depositing the metal.
In the step (2), the chemical deposition speed is increased along with the increasing of the content of copper and silver ions, but in order to stabilize the deposition solution, the concentration of the copper and silver ions is 0.05-0.5 mol/L;
in the step (2), the sodium hydroxide is a speed regulator, the reduction speed is accelerated along with the increase of alkalinity, the plating solution is self-decomposed when the reduction speed is too high, and the concentration of the sodium hydroxide is 0-0.5 mol/L, preferably 0.1-0.5 mol/L;
in the step (2), the ammonia water is beneficial to the stability of copper complex ions and silver complex ions, the concentration of the ammonia water is improved, the stability of ammonia complex ions is increased, and the molar ratio of free ammonia to ammonia complex ions is 1: 1-10: 1;
in the step (2), the reducing agent is formaldehyde, glucose, tartrate or hydrazine sulfate; the reduction speed is formaldehyde, glucose, tartrate and hydrazine sulfate, and for the same reducing agent, the concentration is low, the chemical plating speed is slow and too high, the reduction speed is increased sharply, the self-decomposition of the plating solution is easily caused, metal is separated out in the plating liquid phase, and the molar ratio of the reducing agent to the ammonia complex ion is 1: 1-10: 1.
In the step (2), the deposition pool with the ultrasonic function is self-ultrasonic or the deposition pool is placed in an ultrasonic pool.
In the step (2) of the invention, the copper loading capacity of the prepared crystalline silver of the copper-silver-loaded alloy particles is 1-100mg/g, and the silver loading capacity is 1-100 mg/g.
The invention can obtain high-quality 40% glyoxal product with high yield, the formaldehyde content in the product is lower than 500ppm, and the hydroxy acetaldehyde content is lower than 0.5%. The method is characterized in that the crystalline silver loaded with the copper-silver alloy particles is used as a catalyst, namely the crystalline silver subjected to high-temperature treatment under steam is used as a carrier, the copper-silver alloy particles are loaded on the crystalline silver by a method similar to chemical plating under the ultrasonic condition, namely, copper ions and silver ions are subjected to redox action in the same solution by virtue of a reducing agent under the condition of no current passing, so that the alloy particles of metal copper and metal silver reduced by the ions are deposited on the surface of the carrier. The chemical plating solution consists of metal ion solution and reductant solution, and the adopted proportion and corresponding working condition make the reaction only limited to the surface of the crystal silver carrier with catalytic action, but the reaction does not occur spontaneously in the solution body and on the container wall.
The crystallized silver catalyst of the copper-silver-loaded alloy prepared by the method has the remarkable advantages that: firstly, after electrolytic silver is subjected to high-temperature treatment under steam, crystal faces are reconstructed, and the catalyst has better selectivity and larger surface area and provides a proper active surface for supporting copper-silver alloy; secondly, the ultrasonic action is introduced in the chemical plating process, so that the nucleation speed of metal is greatly accelerated, copper-silver alloy particles can be uniformly deposited on the surface of the pretreated crystallized silver, and the particles have good activity and selectivity at low temperature, so that a high-quality glyoxal product can be directly prepared; thirdly, the thermal conductivity of the catalyst is very good because the carrier is electrolytic silver; fourthly, the catalyst is easy to regenerate and can be regenerated by the same method as the electrolytic silver; fifthly, the macroscopic state of the catalyst is the same as that of the electrolytic silver, so that the catalyst can be conveniently used for replacing the electrolytic silver for industrial application.
Detailed Description
Example 1
Firstly, pretreating electrolytic silver catalyst, charging 5 g of electro-crystallized silver catalyst into a stainless steel reactor with diameter of 14mm, pumping distilled water into a gasifier by a metering pump for vaporization, mixing with preheated air, heating, and then entering into a reaction section for pretreating electrolytic silver, wherein liquid hourly space velocity of distilled water is 20hr-1Air flow rate of 0.035M3The pretreatment temperature is 600 ℃, the steam is stopped after the treatment time is 8 hours, and the mixture is cooled and dried under the air flow.
Dissolving copper nitrate and silver nitrate in distilled water to prepare a solution containing 0.05mol/L of copper nitrate and 0.45mol/L of silver nitrate, then slowly adding ammonia water while stirring to generate copper hydroxide and silver hydroxide precipitates, and adding excessive ammonia water to form a blue mixed solution of a copper ammonia complex and a silver ammonia complex, wherein the molar ratio of excessive ammonia to ammonia complex ions is 1. Adding a reducing agent formaldehyde into the other distilled water solution, wherein the molar ratio of the formaldehyde to the ammonia complex ion is 2, and adjusting the alkalinity by using NaOH to ensure that the concentration of the NaOH is 0.4 mol/L. And mixing the two solutions uniformly to obtain the chemical plating solution. And putting the pretreated crystalline silver into chemical plating solution, starting ultrasound to carry out chemical deposition, and controlling the deposition amount of the silver to be 95mg/g and the deposition amount of the copper to be 8 mg/g. Filtering and drying the plated copper-silver-loaded crystalline silver, and roasting at 650 ℃ for 5 hours to obtain the copper-silver-alloy-loaded crystalline silver catalyst.
5 g of catalyst are loaded in 4 layers into a stainless steel reactor with a diameter of 14mm, the particle size and weight percentages of which are (from top to bottom): the first layer is 0.2-0.4mm, 20%; the second layer is 0.4-0.75mm, 20%; the third layer is 0.7-1.0mm, 40%; the fourth layer is 1.0-2.5mm, 20%. The thickness of each layer of catalyst is the same, and the total thickness of the catalyst is 10-100mm, preferably 20-60 mm. Pumping ethylene glycol water solution into gasifier with metering pump, mixing with preheated air and nitrogen, heating, and reacting in catalytic bed at liquid hourly space velocity of ethylene glycol of 50hr－1The molar ratio of oxygen to glycol is 1.35, the molar ratio of nitrogen to oxygen is 25, the molar ratio of water to oxygen is 5, the reaction temperature is 600 ℃, the product is quenched and then is sprayed and absorbed, the sprayed supplementary water amount is controlled, 40% of glyoxal product is obtained, the conversion rate of the glycol is 100%, the selectivity of methylglyoxal is 82.5%, the formaldehyde content is 200ppm, the hydroxy acetaldehyde content is 0.4%, and the service life of the catalyst is 150 days.
Example 2
The electrolytic silver was pretreated in a similar manner to example 1, with a liquid hourly space velocity of distilled water of 10hr-1Air flow rate of 0.020M3And/h, the pretreatment temperature is 300 ℃, the steam is stopped after the treatment time is 36 hours, and the mixture is cooled and dried under the air flow.
Dissolving copper nitrate and silver nitrate in distilled water to prepare a solution containing 0.45mol/L of copper nitrate and 0.05mol/L of silver nitrate, then slowly adding ammonia water while stirring to generate copper hydroxide and silver hydroxide precipitates, and adding excessive ammonia water to form a blue mixed solution of a copper ammonia complex and a silver ammonia complex, wherein the molar ratio of excessive ammonia to ammine complex ions is 1. Adding a reducing agent tartrate into the other distilled water solution, wherein the molar ratio of the tartrate to the ammonia complex ion is 2, and adjusting the alkalinity by using NaOH to ensure that the concentration of the NaOH is 0.4 mol/L. And (3) uniformly mixing the two solutions to obtain the chemical plating solution, putting the treated crystalline silver into the chemical plating solution, starting ultrasound to deposit, and controlling the deposition amount of copper to be 15mg/g when the deposition amount of copper is 95mg/g of catalyst. Filtering and drying the plated copper-silver-loaded crystalline silver, and roasting at 550 ℃ for 5 hours to obtain the copper-alloy-loaded crystalline silver catalyst.
5 g of catalyst are loaded in three layers into a stainless steel reactor with a diameter of 14mm, the particle size and weight percentage of which are (from top to bottom): the first layer is 0.2-0.4mm, 20%; the second layer is 0.4-1.0mm, 60%; the third layer is 1.0-2.5mm and 20 percent. Pumping ethylene glycol water solution into gasifier with metering pump, mixing with preheated air, heating, and reacting in catalytic bed at liquid hourly space velocity of ethylene glycol of 10hr－1The molar ratio of oxygen to glycol is 0.8, the molar ratio of nitrogen to oxygen is 5, the molar ratio of water to oxygen is 5, the reaction temperature is 450 ℃, the product is quenched and then is sprayed and absorbed, the sprayed supplementary water amount is controlled, 40% of glyoxal product is obtained, the conversion rate of the glycol is 98.3%, the selectivity of methylglyoxal is 73.5%, the formaldehyde content is 300ppm, the hydroxyacetaldehyde content is 0.2%, and the service life of the catalyst is 90 days.
Example 3
The electrolytic silver was pretreated in a similar manner to example 1, with a liquid hourly space velocity of distilled water of 50hr-1Air flow of 0.055M3And/h, the pretreatment temperature is 500 ℃, the steam is stopped after the treatment time is 12 hours, and the mixture is cooled and dried under the air flow.
Dissolving copper nitrate and silver nitrate in distilled water to prepare a solution containing 0.1mol/L of copper nitrate and 0.1mol/L of silver nitrate, then slowly adding ammonia water while stirring to generate copper hydroxide and silver hydroxide precipitates, and adding excessive ammonia water to form a blue mixed solution of a copper ammonia complex and a silver ammonia complex, wherein the molar ratio of excessive ammonia to ammine complex ions is 10. Adding reducing agent glucose into the solution, wherein the molar ratio of the glucose to the ammine complex ions is 9, and uniformly mixing to obtain the chemical plating solution. Putting the pretreated crystalline silver into chemical plating solution, starting ultrasound to carry out chemical deposition, and controlling the deposition amount of the silver to be 50mg/g and the deposition amount of the copper to be 20 mg/g. Filtering and drying the plated copper-silver-loaded crystalline silver, and roasting at 450 ℃ for 4 hours to obtain the copper-silver-alloy-loaded crystalline silver catalyst.
5 g of catalyst are loaded in 5 layers into a stainless steel reactor with a diameter of 14mm, the particle size and weight percentage of which are (from top to bottom): the first layer is 0.2-0.4mm, 20%; the second layer is 0.4-0.6mm, 20%; the third layer is 0.6-0.8mm, 20%; the fourth layer is 0.8-1.0mm, 20%; the fifth layer is 1.0-2.5mm, 20%. Pumping ethylene glycol into gasifier with metering pump, mixing with preheated air and water vapor, and reacting in catalytic bed at liquid hourly space velocity of ethylene glycol of 30hr－1The molar ratio of oxygen to ethylene glycol is 1.1, the molar ratio of nitrogen to oxygen is 15, the molar ratio of water to oxygen is 5, the reaction temperature is 550 ℃, the conversion rate of ethylene glycol is 100%, the selectivity of glyoxal is 83.1%, the formaldehyde content is 100ppm, the hydroxyacetaldehyde content is 0.3%, and the service life of the catalyst is 100 days.
Example 4
The electrolytic silver was pretreated in a similar manner to example 1, with a liquid hourly space velocity of distilled water of 30hr-1Air flow of 0.010M3And/h, the pretreatment temperature is 400 ℃, the steam is stopped after the treatment time is 24 hours, and the mixture is cooled and dried under the air flow.
Dissolving copper nitrate and silver nitrate in distilled water to prepare a solution containing 0.3mol/L of copper nitrate and 0.1mol/L of silver nitrate, then slowly adding ammonia water while stirring to generate copper hydroxide and silver hydroxide precipitates, and adding excessive ammonia water to form a blue mixed solution of a copper ammonia complex and a silver ammonia complex, wherein the molar ratio of excessive ammonia to ammine complex ions is 5. Adding a reducing agent hydrazine sulfate into the solution, wherein the molar ratio of the hydrazine sulfate to the ammine complex ions is 5, and uniformly mixing to obtain the chemical plating solution. Putting the pretreated crystalline silver into chemical plating solution, starting ultrasound to carry out chemical deposition, and controlling the deposition amount of the silver to be 20mg/g and the deposition amount of the copper to be 21 mg/g. Filtering and drying the plated copper-silver-loaded crystalline silver, and roasting at 500 ℃ for 3 hours to obtain the copper-silver-alloy-loaded crystalline silver catalyst.
5 g of catalyst were charged into a stainless steel reactor having a diameter of 14mm, and ethylene glycol was pumped by means of a metering pumpFeeding into gasifier, mixing with preheated air and water vapor, and reacting in catalyst bed at ethylene glycol liquid hourly space velocity of 10hr－1The molar ratio of oxygen to glycol is 0.9, the inert gas is argon, the molar ratio of argon to oxygen is 10, the molar ratio of water to oxygen is 5, the reaction temperature is 420 ℃, the conversion rate of glycol is 99.9%, the selectivity of glyoxal is 80.3%, the content of formaldehyde is 400ppm, the content of hydroxyacetaldehyde is 0.1%, and the service life of the catalyst is 80 days.
Claims (8)
1. A method for synthesizing glyoxal with low impurity content by gas phase oxidation is characterized by comprising the following steps:
(1) placing the crystallized silver in a fixed bed reactor or a tubular furnace for heat treatment, filling the crystallized silver in a reaction section, pumping distilled water into a gasifier by a metering pump to form steam, mixing the steam with preheated air, performing overheating and temperature rise, and then entering the reaction section for pretreating electrolytic silver, wherein the liquid hourly space velocity of the distilled water is 10-50hr-1The air flow rate is 0.002-0.011M per gram of crystalline silver3The pretreatment temperature is 300 ℃ and 600 DEG CThe treatment time is 8-36 hours; stopping steam after the heat treatment is finished, then cooling the electrolytic silver under the air flow, and in the process, driving out the water vapor in the reactor or the tubular furnace to finally obtain dry treated electrolytic silver;
(2) placing the treated electrolytic silver in a deposition pool with an ultrasonic function to carry out metal particle chemical deposition; washing and drying the deposited copper-silver-loaded crystalline silver, and roasting at 400-700 ℃ for 2-6 hours to obtain copper-silver alloy particle-loaded crystalline silver;
the plating solution for chemical deposition consists of copper ammine complex ions, silver ammine complex ions, sodium hydroxide, ammonia water and a reducing agent;
(3) taking the crystallized silver loaded with the copper-silver alloy particles as a catalyst, and carrying out oxidation reaction on ethylene glycol, oxygen, water and inert gas on the catalyst at 400-800 ℃ to generate glyoxal; wherein,
the ethylene glycol is subjected to oxidation reaction in the presence of inert gas, and the molar ratio of the inert gas to oxygen is not less than 4.4: 1; the molar ratio of oxygen to ethylene glycol is 0.7: 1-1.4: 1; the liquid hourly space velocity of ethylene glycol on the catalyst is 5-50 hr-1；
The grain size of the crystallized silver is 0.1-2.5mm, and the crystallized silver is paved into 2 layers or multiple layers according to the grain size.
2. The method for synthesizing glyoxal with low impurity content by gas phase oxidation according to claim 1, wherein in the step (2), the electroless deposition plating solution is prepared by the following specific steps:
(a) dissolving copper nitrate and silver nitrate in distilled water, and adding excessive ammonia water while stirring after the copper nitrate and the silver nitrate are completely dissolved to form a mixed solution of a copper ammonia complex and a silver ammonia complex;
(b) adding a reducing agent into distilled water, adding sodium hydroxide if necessary, and stirring for dissolving;
(c) and mixing the two solutions to obtain the chemical plating solution for depositing the metal.
3. The method for synthesizing glyoxal with low impurity content by gas phase oxidation according to claim 2, wherein in the step (2), the rate of the chemical deposition increases as the content of copper and silver ions increases, but the concentration of copper and silver ions is controlled to be 0.05 to 0.5mol/L for stabilizing the deposition solution.
4. The method for synthesizing glyoxal with low impurity content by gas phase oxidation according to claim 2, wherein in the step (2), the sodium hydroxide is a rate regulator, and the concentration of the sodium hydroxide is controlled to be 0-0.5 mol/L.
5. The method for synthesizing glyoxal with low impurity content by gas phase oxidation according to claim 2, wherein in the step (2), the ammonia water is beneficial to the stability of copper ammine complex ions and silver ammine complex ions, and the molar ratio of free ammonia to ammine complex ions is controlled to be 1: 1-10: 1.
6. The process for preparing glyoxal with low impurity content by gas phase oxidation according to claim 2, wherein in the step (2), the reducing agent is formaldehyde, glucose, tartrate or hydrazine sulfate; the molar ratio of the reducing agent to the ammonia complex ion is controlled to be 1: 1-10: 1.
7. The process for preparing acetaldehyde with low impurity content by gas phase oxidation according to claim 1, wherein in the step (2), the deposition tank with ultrasonic function is self-ultrasonic or the deposition tank is placed in an ultrasonic tank.
8. The process according to claim 1, wherein in step (2), the copper-loaded silver alloy particles are prepared with crystalline silver, the copper loading in the alloy is 1-100mg/g, and the silver loading is 1-100 mg/g.
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| CN104645983A (en) * | 2015-01-28 | 2015-05-27 | 复旦大学 | Catalyst for cycling gas purification in process for producing glyoxal by air oxidation of ethylene glycol as well as preparation method and application thereof |
| CN105562048A (en) * | 2015-12-16 | 2016-05-11 | 湖北省宏源药业科技股份有限公司 | Cerium, rhenium and phosphorus modified electrolytic silver catalyst as well as preparation method and application of cerium, rhenium and phosphorus modified electrolytic silver catalyst |
| CN105712855A (en) * | 2016-01-04 | 2016-06-29 | 临沂市金沂蒙生物科技有限公司 | Decoloration method and device for producing glyoxal by using glyoxal catalytic oxidation method |
| CN110002973A (en) * | 2019-04-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation process preparing glyoxal based on glycol catalytic oxidation |
| CN116082130A (en) * | 2023-02-03 | 2023-05-09 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
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| CN105562048A (en) * | 2015-12-16 | 2016-05-11 | 湖北省宏源药业科技股份有限公司 | Cerium, rhenium and phosphorus modified electrolytic silver catalyst as well as preparation method and application of cerium, rhenium and phosphorus modified electrolytic silver catalyst |
| CN105562048B (en) * | 2015-12-16 | 2017-12-12 | 湖北省宏源药业科技股份有限公司 | Catalyst for electrolytic silver that a kind of caesium, rhenium, phosphorus are modified and its preparation method and application |
| CN105712855A (en) * | 2016-01-04 | 2016-06-29 | 临沂市金沂蒙生物科技有限公司 | Decoloration method and device for producing glyoxal by using glyoxal catalytic oxidation method |
| CN105712855B (en) * | 2016-01-04 | 2019-05-14 | 临沂市金沂蒙生物科技有限公司 | The discoloration method and device of glycol catalytic oxidation method production glyoxal |
| CN110002973A (en) * | 2019-04-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation process preparing glyoxal based on glycol catalytic oxidation |
| CN116082130A (en) * | 2023-02-03 | 2023-05-09 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
| CN116082130B (en) * | 2023-02-03 | 2024-03-29 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
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